Fluoroborane salts comprising a reactive cation and uses thereof

ABSTRACT

The present invention provides weakly coordinating anion salts comprising a reactive cation and uses thereof. In particular, the present invention provides compounds of the formula M x Q y  and uses thereof, where M, Q, x, and y are those defined herein.

FIELD OF THE INVENTION

[0001] The present invention relates to weakly coordinating anion saltscomprising a reactive cation and uses thereof. In particular, thepresent invention relates to fluoroborate salts comprising a reactivecation. Specifically, the present invention provides compounds of theformula M_(x)Q_(y), where M, Q, x, and y are those defined herein.

BACKGROUND OF THE INVENTION

[0002] Weakly coordinating anion salts comprising a reactive cation areuseful in variety of reactions including polymerization reactions,coupling reactions, and other chemical reactions which is facilitated byan appropriate cation. Useful reactive cations include silver cation,silylium cations, aluminum cations, ammonium cations, protonated arenes,triaryl carbocation, and other cations which can facilitate a chemicalreaction such as a polymerization reaction, coupling reaction, and othercatalytic reactions.

[0003] Currently, there are no methods to generate stable reactivecations, such as cation-like aluminum (i.e., pseudo aluminum-cation)species, e.g., AlMe₂ ⁺¹, in the presence of weakly coordinating anions(WCA's). For example, when the AlMe₂ ³⁰ ¹ was generated in situ, itcaused the rapid decomposition of one of the most efficient WCA's known,viz. B(C₆F₅)₄ ⁻¹ (Al(C₆F₅)₃ was one of the reaction products).¹ Othercationic aluminum complexes are based on the use of bulky nitrogenligands to stabilize the positive charge on the aluminum atom. Thesynthesis and characterization of aluminum alkyl complexes containingguanidimates, ² amidinates, ³ aminotroponimates, ⁴ andpyridyliminoamide⁵ ligands have recently been reported. These complexesexhibited ethylene polymerization activity of 900-2, 600 gPE/(mol.atm.h) in toluene at 80 to 100° C. and 1 to 5 atm ofethylene.^(1, 4) However, the steric or electronic properties of thenitrogen ligands may disfavor the coordination and activation of largeorganic molecules. The synthesis of π-stabilized (η⁵-Cp*)₂Al⁺¹ has alsobeen reported.⁶

[0004] In addition, it is believed no examples of C—H activation bycationic aluminum complexes has been reported. However, η¹-arene complexof Al(C₆F₅)₃ has recently been reported⁷, which may represent a modelfor the first step in C—H activation of aromatic molecules by aluminumcationic complexes. The catalytic activation of aromatic C—H bondsresulting in arene-olefin coupling is of considerable current interestfor chemical and pharmaceutical industries.^(8, 9) Efficientpalladium-catalyzed oxidative coupling of arenes with olefins hasrecently been reported.⁸ Other methods of arene-olefin coupling includeuse of strong Lewis acids (e.g., AlCl₃) and Bronsted acids (e.g., HF,BF₃.HF, and AlCl₃.HCl).¹⁰ However these methods are usually accompaniedby isomerization, disproportionation, and transalkylation. In addition,the use of WCA's other than fluorocarborate anions such as 1-R—CB₁₁F₁₁⁻¹ to generate AlMe₂ ⁺¹ cation-like species has resulted in rapiddecomposition of the aluminum cation as well as the WCA. Furthermore, itis believed that no other stable aluminum compound can catalyze C—Hactivation in the absence of a strong Bronsted acid.

[0005] Furthermore, many conventional co-catalysts for an α-olefin(e.g., ethylene) polymerization, including methylalurnoxane (MAO), havelimited solubilities in aliphatic hydrocarbon solvents and are notstable when stored in solution.¹¹

[0006] Therefore, there is a need for stable weakly coordinating anionsalts comprising a reactive cation that are useful in variety of organicreactions.

SUMMARY OF THE INVENTION

[0007] The present invention provides a compound of the formula:

M_(x)Q_(y)   I

[0008] where each M is independently a cation, provided at least one Mis a reactive cation. Preferably, M is selected from the groupconsisting of silver cation, aluminum cations, silylium cations,ammonium cations, protonated arenes, and triaryl carbocation. Q is aweakly coordinating anion (i.e., WCA). Preferably, Q is apolyhalogenated polyhedral borate or a fluorinated WCA, and morepreferably a polyhalogenated polyhedral borate or a fluorinatedpolyhedral borate moiety selected from the group consisting ofmonoheteroborate and aminoborate. Preferably, when Q is amonoheteroborate then M is an aluminum cation. The variable x is anabsolute value of the oxidation state of Q, i.e., when the oxidationstate of Q is −1, then x is 1, and similarly when the oxidation state ofQ is −2, then x is 2. Preferably, the oxidation state of Q is −1 or −2.And the variable y is an absolute value of the oxidation state of M. Itshould be appreciated that when there is more than one type of M ispresent in the Compound of Formula I, the variable y is the absolutevalue of the total oxidation states of all M's present. And similarly,when there is more than one type of Q is present in the Compound ofFormula I, the variable x is the absolute value of the total oxidationstates of all Q's present.

[0009] Preferably, the aluminum cation is a moiety of the formula(R¹R²Al)⁺¹, where each of R¹ and R² is independently selected from thegroup consisting of alkyl, cycloalkyl, aryl, aralkyl, cycloalkalkyl,alkenyl, and halide. Preferably, each of R¹ and R² is independentlyselected from the group consisting of alkyl, aryl, and halide. And morepreferably, each of R¹ and R² is independently selected from the groupconsisting of methyl, ethyl, iso-propyl, propyl, butyl, iso-butyl,t-butyl, pentyl, hexyl, and halide.

[0010] Preferably, the silylium cation is a moiety of the formula(R³R⁴R⁵Si)⁺¹, where each of R³, R⁴, and R⁵ is independently selectedfrom the group consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl,and halide. More preferably, each of R³, R⁴, and R⁵ is independentlyselected from the group consisting of hydrogen, alkyl, and aryl. Andmost preferably, each of R³, R⁴, and R⁵ is independently selected fromthe group consisting of alkyl and aryl.

[0011] Preferably, the ammonium cation is a moiety of the formula(R¹⁶R¹⁷R¹⁸NH)⁺¹, where each of R¹⁶, R¹⁷, and R¹⁸ is independentlyselected from the group consisting of hydrogen, alkyl, aryl, aralkyl,cycloalkyl, and silyl. Preferably, each of R¹⁶, R¹⁷, and R¹⁸ isindependently selected from the group consisting of alkyl, aryl,aralkyl, and cycloalkyl. More preferably, R¹⁶, R¹⁷, and R¹⁸ are alkyl.

[0012] Preferably, the protonated arene is a moiety of the formula(Ar¹H)⁺¹, where Ar¹ is an optionally substituted aryl. In one embodimentof the present invention, Ar¹ is phenyl.

[0013] Preferably, the triaryl carbocation is a moiety of the formula(Ar²Ar³Ar⁴C)⁺¹, where each of Ar², Ar³, and Ar³ is independently anoptionally substituted aryl. In one embodiment of the present invention,Ar², Ar³, and Ar³ are phenyl (i.e., the triaryl carbocation is tritylcation).

[0014] Preferably, the monoheteroborate anion is of the formula((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f))⁻¹, where R⁶ is bonded to Z, Zis bonded to B, and each of H, F, X, and OR⁷ is bonded to a differentboron atom. R⁶ is selected from the group consisting of polymer,hydrogen, halide, alkyl, silyl, cycloalkyl, alkenyl, alkynyl, and aryl.Preferably, R⁶ is selected from the group consisting of alkyl, aryl, andsily. More preferably R⁶ is selected from the group consisting ofmethyl, ethyl, dodecyl, butyl, iso-butyl, t-butyl, silyl, propyl,iso-propyl, pentyl, hexyl, and a polymer. Z is selected from the groupconsisting of C, Si, Ge, Sn, Pb, N, P, As, Sb, and Bi. Preferably Z isC. Each X is independently halide. R⁷ is selected from the groupconsisting of polymer, hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl,and aryl. The variable “a” is 0 or, preferably, 1. The variable “b” isan integer from 5 to 13, preferably 11. The variable “c” is an integerfrom 0 to 12, preferably c” is 0. The variable “d” is an integer from 2to 13, preferably 11. The variable “e” is an integer from 0 to 11,preferably 0. And the variable “f” is an integer from 0 to 5, preferably0. The sum of c+d+e+f is b.

[0015] Preferably, the aminoborate anion is a moiety of the formula(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i))⁻¹, where R⁸, R⁹, and R¹⁰ are bonded to N, andN is bonded to boron, and each of H and F is bonded to a different boronatom. Each of R⁸, R⁹, and R¹⁰ is independently selected from the groupconsisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl, and a polymer.Preferably, R⁸, R⁹, and R¹⁰ are alkyl. The variable “g” is an integerfrom 6 to 14, preferably 12. The variable “h” is an integer from 0 to13, preferably 0. The variable “i” is an integer from 1 to 14,preferably 11. And the sum of 1+h+i is g.

[0016] Preferably, the polyhalogenated borate anion is a moiety of theformula (B₁₂X₁₂)⁻², where each X is independently halide. Preferably thehalide of polyhalogenated borate is selected from the group consistingof Cl and F. In one particular embodiment of the present invention, thepolyhalogenated borate comprises at least three fluorine atoms,preferably at least 6 fluorine atoms, more preferably at least 11fluorine atoms, and most preferably all of the X are fluorine atoms.

[0017] One particular embodiment of the present invention provides acompound of the formula:

M¹ _(m)(R¹R²Al)_(n)Q_(q)   IA

[0018] where R¹, R², and Q are those defined above; M¹ is a non-reactivecation; m is 0 or 1; n is 1 or 2, provided that the sum of m and n is anabsolute value of the oxidation state of Q; and q is an absolute valueof the total oxidation state of M¹ and (R¹R¹Al), preferably q is 1 or 2,and more preferably q is 1.

[0019] Another aspect of the present invention provides a catalystcomponent comprising the Compound of Formula I.

[0020] In one particular embodiment of the present invention, thecatalyst component comprises a compound selected from compounds of theformula:

[0021] (i) (R¹R²Al)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f));

[0022] (ii) (R³R⁴R⁵Si)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f));

[0023] (iii) (R¹⁶R¹⁷R¹⁸NH)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f))

[0024] (iv) (Ar¹H)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f));

[0025] (v) (Ar²Ar³Ar⁴C)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)); and

[0026] (vi) Ag((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)),

[0027] where Ar¹, Ar², Ar³, Ar⁴, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁶, R¹⁷,R¹⁸, Z, X, a, b, c, d, e, and f are those defined above.

[0028] In another embodiment of the present invention, the catalystcomponent comprises a compound selected from compounds of the formula:

[0029] (i) (R¹R²Al)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i));

[0030] (ii) (R³R⁴R⁵Si)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i));

[0031] (iii) (R¹⁶R¹⁷R¹⁸NH)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i))

[0032] (iv) (Ar¹H)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i));

[0033] (v) (Ar²Ar³Ar⁴C)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)); and

[0034] (vi) Ag(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)),

[0035] where Ar¹, Ar², Ar³, Ar⁴, R¹, R², R³, R⁴, R⁵, R⁸, R⁹, R¹⁰, R¹⁶,R¹⁷, R¹⁸, g, h, and i are those defined above.

[0036] Yet in another embodiment of the present invention, the catalystcomponent comprises a compound selected from compounds of the formula:

[0037] (i) (M¹)_(m)(R¹R²Al)_(n)(B₁₂X₁₂);

[0038] (ii) (M¹)_(m)(R³R⁴R⁵Si)_(n)(B₁₂X₁₂);

[0039] (iii) (M¹)_(m)(R¹⁶R¹⁷R¹⁸NH)_(n)(B₁₂X₁₂)

[0040] (iv) (M¹)_(m)(Ar¹H)_(n)(B₁₂X₁₂);

[0041] (v) (M¹)_(m)(Ar²Ar³Ar⁴C)_(n)(B₁₂X₁₂); and

[0042] (vi) (M¹)_(m)Ag_(n)(B₁₂X₁₂),

[0043] where Ar¹, Ar², Ar³, Ar⁴, R¹, R², R³, R⁴, R⁵, R¹⁶, R¹⁷, R¹⁸, M¹,X, m, and n are those defined above.

[0044] Still another aspect of the present invention provides a processfor preparing an olefin polymer by polymerization of at least one olefincompound in the presence of a catalyst component, where the catalystcomponent comprises the Compound of Formula I described above.Preferably, the olefin is an α-olefin.

[0045] Yet another aspect of the present invention provides anarene-olefin coupling process using the Compound of Formula IA.

[0046] Still another aspect of the present invention provides a methodfor preparing the Compound of Formula I.

BRIEF DESCRIPTION OF THE DRAWINGS

[0047]FIG. 1 is an x-ray crystal structure of[Al(CH₃)₂(1-CH₃—CB₁₁F₁₁)]₂;

[0048]FIG. 2 is an x-ray crystal Structure of (CPh₃)₂B₁₂F₁₂; and

[0049]FIG. 3 is an x-ray crystal Structure of Si(i-Pr)₃(1-Et—CB₁₁F₁₁)

DETAILED DESCRIPTION OF THE INVENTION

[0050] The term “alkyl” refers to aliphatic hydrocarbons which can bestraight or branched chain groups. Preferably an alkyl group has one toabout twenty carbon atoms. Alkyl groups optionally can be substitutedwith one or more substituents, such as a halogen, alkenyl, alkynyl,aryl, hydroxy, amino, thio, alkoxy, carboxy, oxo or cycloalkyl. Theremay be optionally inserted along the alkyl group one or more oxygen,sulfur or substituted or unsubstituted nitrogen atoms. Exemplary alkylgroups include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl,pentyl, octyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl,chloromethyl, trichloromethyl, pentafluoroethyl, and the like.

[0051] The term “halo, ” “halide” or “halogen, ” when referring to asubstituent means fluoro, chloro, bromo, or iodo, preferably chloro orfluoro.

[0052] The term “cycloalkyl” refers to a saturated monovalentsubstituted or unsubstituted mono- or bicyclic hydrocarbon orheterocyclyl radical, preferably of three to twenty carbon atoms.Cycloalkyl may contain one, two or three substituents which are nothydrogen. Exemplary cycloalkyls include, but are not limited to,substituted or unsubstituted cyclopropyl, cyclopentyl, cyclohexyl,cyclooctyl, bicyclodecyl, and the like.

[0053] The terms “aryl” and “arene” refers to a monovalent monocyclic orbicyclic aromatic hydrocarbon radical which is optionally substitutedwith one or more substituents, preferably of five to 20 carbon atoms.Exemplary aryls or arenes include, but is not limited to, substituted orunsubstituted phenyl, substituted or unsubstituted 1-naphthyl,2-naphthyl, and the like.

[0054] The term “heterocyclyl” means a substituted or unsubstitutedsaturated cyclic radical in which one or two ring atoms are heteroatomsselected from the group consisting of N, O, or S(O)_(n) (where n is aninteger from 0 to 2), the remaining ring atoms being C. The heterocyclylring may be optionally substituted independently with one, two, or threesubstituents such as alkyl, alkoxy, and aryl groups.

[0055] As used herein, the term “heteroalkyl” means a branched orunbranched, cyclic or acyclic saturated alkyl radical containing carbon,hydrogen and one or more heteroatoms in place of a carbon atom, oroptionally one or more heteroatom-substituents containing carbon atom.

[0056] The term “aralkyl” means a radical —R^(a)R^(b) where R^(a) is analkylene group and R^(b) is an aryl group as defined above, e.g.,benzyl, phenylethyl, and the like.

[0057] The term “cycloalkylalkyl” means a radical —R^(a)R^(b) whereR^(a) is an alkylene group and R^(b) is a cycloalkyl group as definedabove, e.g., cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, andthe like.

[0058] The terms “alkoxy”, “aryloxy”, “aralkyloxy”, and“heteroaralkyloxy” mean a radical —OR where R is an alkyl, aryl,aralkyl, and heteroaralkyl, respectively, as defined above, e.g.,methoxy, phenoxy, pyridin-2-ylmethyloxy, benzyloxy, and the like.

[0059] The term “reactive cation” refers to a cation which canfacilitate a chemical reaction such as a polymerization reaction,coupling reaction, and other catalytic reactions. Exemplary reactivecations include silver cation, aluminum cations, silylium cations,ammonium cations, protonated arenes, and triaryl carbocation.

[0060] The term “weakly coordinating anion” refers to the anion whichweakly coordinates to a reactive cation and can be easily displaced fromthe cation by neutral donor molecules.

[0061] The term “pseudohalide” refers to moieties which are not halidesbut are generally considered to be a good leaving group in asubstitution reaction. Exemplary pseudohalides include isocyanate,cyanide, tosylate, mesylate, acetate, and the like.

[0062] Unless otherwise defined, the term “silyl” refers to a moiety ofthe formula R^(a)R^(b)R^(c)Si—, where each of R^(a), R^(b), and R^(c) isindependently hydrogen, alkyl, aryl, aralkyl, or cycloalkyl.

[0063] The present invention provides salts comprising a weaklycoordinating anion and a reactive cation, and catalyst componentscomprising the same. The present invention also provides methods forpreparing these salts as well as methods for using these salts. Inparticular, the present invention provides fluoroborate salts comprisinga reactive cation.

[0064] In one aspect, the present invention provides compounds of theformula:

M_(x)Q_(y)   I

[0065] where M, Q, x, and y are those defined above. It should beappreciated that when the oxidation state of Q is −2, then x is 2. Insuch cases, more than one M moiety can be present. Preferably at leastone M moiety is a reactive cation. The other M moiety can be any cationsuch as an alkaline metal (e.g., Li, Na, K, Rb, Cs, or Fr) or atransition metal cation (e.g., Cu⁺¹, Ag⁺¹, Ni⁺², Zn⁺², Pd⁺²)

[0066] One aspect of the present invention provides cations comprisingan aluminum, which are useful in a variety of organic reactions,including as catalysts for the activation of carbon-hydrogen bonds andas co-catalysts for the polymerization of olefins, in particular,α-olefins such as ethylene. The present invention also provides a methodfor preparing the same.

[0067] In one embodiment, the present invention provides a compound ofthe formula:

M¹ _(m)(R¹R²Al)_(n)Q_(q)   IA

[0068] where R¹, R², Q, M¹, m, n, and q are those defined above.Compound of Formula IA comprises a very chemically robust (i.e., stable)weakly coordinating anion, Q, which does not readily decompose. Inaddition, unlike many other aluminum metal catalysts, Compound ofFormula IA has a relatively high solubility in aliphatic hydrocarbonsolvents. For example, the compound AlMe₂(1-Dd—CB₁₁F₁₁), where Dd isdodecyl, is soluble in hexanes and methylcyclohexane and stable for atleast 10 days at 25° C. Moreover, it has been shown to be a goodco-catalyst for metallocene catalyzed olefin, e.g., ethylene,polymerization.

[0069] Preferably each of R¹ and R² is independently selected from thegroup consisting of alkyl and aryl. More preferably, each of R¹ and R²is independently selected from the group consisting of methyl, ethyl,phenyl, halide, and pseudohalide.

[0070] In one particular embodiment of the present invention, thecompound of the present invention is of the formula:

(R¹R²Al)[(R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)]  II

[0071] where R¹, R², R⁶, R⁷, X, Z, a, b, c, d, e, and f are thosedefined above.

[0072] With respect to Compounds of Formula II:

[0073] Preferably, each X is independently halide. More preferably, X isselected from the group consisting of chloride, iodide, and bromide,still more preferably X is selected from the group consisting ofchloride and bromide, and most preferably X is chloride.

[0074] Preferably, R⁷ is selected from the group consisting of polymer,alkyl, cycloalkyl, and aryl. More preferably, R⁷ is selected from thegroup consisting of polymer, alkyl, and aryl. And most preferably, R⁷ isan alkyl.

[0075] Preferably, a is 1.

[0076] Preferably, b is an integer from 5 to 11. More preferably b is 5,9 or 11, still more preferably b is 9 or 11, and most preferably b is11.

[0077] Preferably, c is an integer from 0 to 7, more preferably from 0to 5, and most preferably 0.

[0078] Preferably d is an integer from 2 to 13, more preferably from 2to 11. Still more preferably d is 5, 9 or 11, yet still more preferablyd is 9, or 11, and most preferably d is 11.

[0079] Preferably, e is an integer from 0 to 11, and more preferablyfrom 0 to 5. Most preferably e is 0.

[0080] Preferably, f is an integer from 0 to 5, more preferably from 0to 4, and most preferably from 0 to 3.

[0081] In another embodiment, the compound of the present invention isof the formula:

(R¹R²Al)[R¹¹R¹²R¹³N—B_(g)H_(h)F_(i)]  III

[0082] where R¹, R², R¹¹, R¹², R¹³, g, h, and i are those defined above.

[0083] With respect to Compounds of Formula III:

[0084] Preferably, each of R¹¹, R¹², and R¹³ is independently selectedfrom the group consisting of hydrogen, methyl, ethyl, butyl, benzyl,hexyl, cyclohexylmethyl, octyl, dodecyl, and silyl.

[0085] Preferably, the variable g is 10 or 12. More preferably g is 12.

[0086] Preferably, h is 0.

[0087] Preferably, i is g-1 (i.e., when g is 10 or 12, i is 9 or 11,respectively).

[0088] Compounds of Formula IA can be prepared by a variety of methods.In one specific example, Compounds of Formula II can be preparedaccording to the following reaction equation:

[0089] Briefly, a trisubstituted aluminum compound (e.g., Compound 1) isreacted with a compound containing a WCA (e.g., Compound 2). One of thesubstituent in the trisubstituted aluminum compound is displaced by theWCA to produce Compound of Formula II (e.g., Compound 3) and acation-substituent coupled product (e.g., Compound 4) which is formedfrom the counter cation (e.g., trityl group in the above equation) ofcompound containing WCA and the displaced substituent of thetrisubstituted aluminum compound.

[0090] Without being bound by any theory, it is believed that the firststep in the reaction is displacement of the counter cation of compoundcontaining WCA by trisubstituted aluminum compound. It is believed thatthe displaced cation then reacts with one of the substituent on thetrisubstituted aluminum moiety to generate Compound of Formula II andthe cation-substituent coupled product. Moreover, it is generallybelieved that stable counter cations of WCA are relatively easilydisplaced by the trisubstituted aluminum compound.

[0091] Because a trisubstituted aluminum compound is generally morereadily available and less expensive than other compounds containingWCA, Compound of Formula IA formation reaction generally uses at least 1equivalents of the trisubstituted aluminum compound relative to thecompound containing WCA. Preferably the amount of trisubstitutedaluminum compound used in Compound of Formaula IA formation reaction isfrom about 1 equivalents to about 15 equivalents, more preferably fromabout 2 equivalents to about 10 equivalents, and most preferably fromabout 2 equivalents to about 5 equivalents.

[0092] When AlMe₂(1-Me—CB₁₁F₁₁), which can be prepared as shown in eq. 1above, was dissolved in toluene-d8, formation of mono-deuteromethane,CH₃D, was observed. Without being bound by any theory, it is believedthat this may have occurred by activation of one of the aromatic C—Dbonds of the solvent C₆D₅CD₃, as shown in the reaction equation below:

AlMe₂(1-Me—CB₁₁F₁₁)+2C₆D₅CD₃→Al(C₆D₄CD₃)₂(1-Me—CB₁₁F₁₁)+2CH₃D

[0093] This reaction constitutes stoichiometric activation of aromaticC—H (in this case C—D) bonds.

[0094] Compounds of Formula IA are useful in a variety of organicreactions including in an arene-olefin coupling reaction. Thus, when theabove reaction was repeated under one atmosphere of ethylene (CH₂═CH₂),a GC-MS analysis of the reaction mixture after 14.5 hr at 24° C.indicated the catalytic formation of all three positional isomers (i.e.,the ortho (47%), meta (35%), and para (18%) isomers) ofC₆D₄(CD₃)(CH₂CH₂D) (the number of turnovers in this particularexperiment was approximately 60-70. Without being bound any theory, theproposed catalytic scheme, which includes the catalytic activation ofaromatic C—H bonds and the catalytic insertion of ethylene into analuminum-aryl bond, is shown in FIG. 1 in a generic scheme using C₆H₆ asthe substrate instead of C₆D₅CD₃ for simplicity (the coordinatedfluorocarborate anion (i.e., Q moiety) has also been omitted from thescheme for simplicity). It should be appreciated that the AlPh₂ ⁺¹species shown in FIG. 1 may in fact be a mixture of AlPh₂ ⁺¹ andAlMePh⁺¹ species.

[0095] When toluene-d₈ was used as the substrate, the aryl aluminummoiety at the top of the central cycle in FIG. 1 is one of the threepossible isomers shown below, which accounts for the three isomers ofC₆D₄(CD₃)(CH₂CH₂D) observed in the GC-MS analysis (R=o-, m-, or p-tolylgroup):

[0096] Thus, another aspect of the present invention provides a processfor coupling an olefin to an aryl compound comprising:

[0097] (a) contacting an aryl compound of the formula:

R¹¹H

[0098] with Compound of Formula IA to form a hydrocarbylaluminum complexselected from the group consisting of a compound of the formula:

M¹ _(m)(R¹R¹¹Al)_(n)Q_(q), M¹ _(m(R) ²R¹¹Al)_(n)Q_(q), M¹_(m)[(R¹¹)₂Al]_(n)Q_(q),

[0099] and mixtures thereof, and

[0100] (b) contacting the hydrocarbylaluminum complex with an olefin ofthe formula:

R¹²R¹³C═CR¹⁴R¹⁵

[0101] to form an alkyl substituted aryl compound of the formula:

R¹¹R¹²R¹³C—CHR¹⁴R¹⁵

[0102] where R¹, R², Q, M¹, m, n, and q are those defined above. Andwhere R¹¹ is an aryl, preferably phenyl, toluyl, or xylyl. PreferablyR¹¹ is substituted or unsubstituted phenyl. Each of R¹², R¹³, R¹⁴ andR¹⁵ is independently selected from the group consisting of hydrogen,alkyl, aryl, cycloalkyl, aralkyl, cycloalkakyl, halide, and a polymer.Preferably, each of R¹², R¹³, R¹⁴ and R¹⁵ is independently selected fromthe group consisting of hydrogen, alkyl, aryl, cycloalkyl, aralkyl,cycloalkakyl, and halide

[0103] The arene-olefin coupling is preferably carried out at atemperature of from about −90° C. to about 300° C., particularlypreferably from about 0 to about 140° C. The reaction pressure is fromabout 100 mmHg to about 100000 mmHg, preferably from about 500 mmHg toabout 10000 mmHg. The arene-olefin can be carried out continuously orbatchwise, in one or more stages, in solution, in suspension, in the gasphase or in a supercritical medium.

[0104] It is also possible to use mixtures of two or more Compounds ofFormula IA. Moreover, the Compounds of Formula IA (or Compounds ofFormula I comprising the polyhedral borate anion, in particular amonoheteroborate) can also be applied to a solid support. Exemplarysolid support materials which are useful in the present inventioninclude, but not limited to, activated carbon, alumina, silica, zeolitesand polymeric supports. Exemplary polymeric supports include polymerresins such as polystyrene, polyethylene, polyurethane, polypropylene,and polytetrafluoroethylene. Typically, in an arene-olefin couplingreaction, the Compound of Formula IA is used in a concentration ofpreferably from about 0.01 mM to about 1 M, more preferably from about 1mM to about 100 mM.

[0105] More generally, Compounds of Formula I can be prepared by:

[0106] (i) fluorinating a non-fluorinated compound of the formula M¹_(p)Q¹ _(q) by contacting the non-fluorinated compound with HF, F₂ ormixtures thereof under conditions sufficient to produce a fluorinatedsalt of the formula M¹ _(p)Q² _(q), where M¹ is that defined above; Q¹is a nonfluorinated polyhedral borate moiety selected from the groupconsisting of monoheteroborate, aminoborate, and polyhalogenated borate;Q² is a fluorinated Q¹; p is an absolute value of the oxidation state ofQ¹; and q is an absolute value of the oxidation state of M¹, and

[0107] (ii) exchanging the non-reactive cation with a reactive cation toproduce a fluorinated salt of the formula M_(p)Q² _(q), where M, Q, p,and q are those defined above.

[0108] Fluorination of a non-fluorinated compound of the formula M¹_(p)Q¹ _(q) are generally described in commonly assigned U.S. patentapplication Ser. No. 09/049, 420, now U.S. Pat. No. 6, 130, 357, issuedOct. 10, 2000, which is incorporated herein by reference in itsentirety. Procedures for fluorinating a non-fluorinated Compound of theFormula M¹ _(p)Q¹ _(q) can also be found in commonly assigned U.S.Patent Application entitled “Fluorinated Amino Polyhedral BoronCompounds”, further identified with Attorney Docket No. 019397-006000US,filed even date herewith, which is incorporated herein by reference inits entirety.

[0109] The work-up of fluorination reaction mixtures typically resultsin the isolation of cesium, potassium, or trimethylammonium salts offluorinated anions. The work-up of alkylation reactions of fluorinatedaminoborate anions usually results in the isolation of cesium ortetraalkylammonium salts. A variety of different methods are availableto convert the above salts into the salts of fluorinated polyhedralborate anions with reactive cations, such as trialkylammonium, silver,triaryl carbocation, silylium, dialkylaluminum and others.Tetraalkylammonium, cesium, and potassium salts of fluorinated borateand carborane anions can be converted into acids H_(x)Q·(solvent)_(z),where _(x) and Q are those defined above and z is the amount ofsolvation, by eluting their solutions through a column packed with acation exchange resin in its acidic form. Suitable solvents include anaqueous solvent and polar organic solvents, such as methanol,acetonitrile and others. The acids H_(x)Q·(solvent) can be neutralizedwith (M³)⁺(OH)⁻(M³=metal) or appropriate amines R¹⁶R¹⁷R¹⁸N, where R¹⁶,R¹⁷ and R¹⁸ are those defined above, to prepare metal salts M³₂Q·(solvent)_(z) or trialkylammonium salts (R¹⁶R¹⁷R¹⁸NH)(Q) offluorinated polyhedral borate anions. Trialkylammonium salts offluorinated polyhedral borate and carborane anions can also be preparedby the metathesis reactions of potassium, cesium, or silver salts offluorinated borate and carborane anions with trialkylammonium halides.The separation of the products from the reaction mixtures is usuallymuch easier if the silver salts of fluorinated borate and carboraneanions are used for the metathesis reactions.

[0110] The silver salts of fluorinated borate and carborane anions canbe prepared by the metathesis reactions of their cesium and potassiumsalts with silver tetrafluoroborate in appropriate organic solvents.Preferably the cesium or potassium salts of fluorinated borate andcarborane anions is soluble in that solvent and cesium or potassiumsalts of tetrafluoroborate anion is insoluble or only very slightlysoluble in that solvent. Suitable solvents for the preparation of silversalts include acetonitrile, dichloromethane, benzene, toluene, ether,tetrahydrofuran and other solvents, which satisfy the aboverequirements. Depending on the solvent, the isolation of the silvercomplexes with solvent molecules or the neat silver salts is possible.

[0111] There are a variety of methods for the syntheses of triarylcarbocation salts with fluorinated polyhedral borate anions. Forexample, the salts of fluorinated polyhedral borate anions comprising anelectophilic cation, such as Li⁺ or Ag⁺, can be treated with a triarylcarbon halide, e.g., CPh₃Cl, in an approptiate organic solvent. Withoutbeing bound by any theory, it is believed that the reaction is based onthe halide abstraction from the triaryl carbon halide by theelectrophilic cation. The insoluble lithium or silver halides areremoved by filtration and triaryl carbcation salts are isolated from thefiltrate. Suitable solvents for the preparation of triaryl carbocationsalts include acetonitrile, dichloromethane, benzene, toluene, ether,tetrahydrofuran and other organic solvents. Alternatively, triarylcarbocation salts can be prepared by the metathesis reactions of cesiumor potassium salts of fluorinated polyhedral borate anions with atriaryl carbocation tetrafluoroborate. Cesium or potassium salts oftetrafluoroborate are removed from the reaction mixtures by filtrationand triaryl carbocation salts of fluorinated borate and carborane anionsare isolated from the filtrate.

[0112] The syntheses of silylium and dialkylaluminum salts offluorinated borate and carborane anions usually require the use of theirtriarylcarbenium salts, preferentially triaryl carbocation salts, as astarting material. The syntheses involve treatment of trialkylsilanesand alkylaluminum compounds with a triaryl carbocation salt offluorinated polyhedral borate anion. Without being bound by any theory,the synthetic strategy is based on the formation of stronger C—H or C—Cbonds compare to relatively weaker Si—H or Al—C bonds. In the reactionsof trityl cation salts with trialkylsilanes, the hydride abstraction bytrityl cation is believed to occur to form triphenylmethane. In thereaction of trityl salts with alkylaluminum compounds, the hydride oralkyl abstractions can occur depending on the structure of alkylaluminumcompound as shown below:

R³R⁴R⁵SiH+(trityl)Q→(R³R⁴R⁵Si)(Q)+(trityl)H

R¹R²AlR¹⁹+(trityl)Q→(R¹R²Al)(Q)+(trityl)R¹⁹

[0113] where R¹, R², R³, R⁴, R⁵, R¹⁹, and Q are those defined above.

[0114] For example:

Me₃Al+CPh₃(Q)→Me₂Al(Q)+CPh₃Me

Et₃Al+CPh₃(Q)→Et₂Al(Q)+CPh₃H+ethylene

[0115] The choice of the solvent facilitates production and isolation ofproducts in the above reactions since the generated silylium anddialkylaluminum cations are highly reactive and typically form strongcomplexes with oxygen or nitrogen containing solvents and also abstracthalogen atoms from halogenated solvents. Preferred solvents includehydrocarbon organic solvents (i.e., compounds having only carbon andhydrogen atoms), such as benzene, toluene, xylene, pentane, hexane,isooctane and others. Preferably, an excess amount of trialkylsilane isused in the preparation of silylium salts of fluorinated polyhedralborate anions.

[0116] Generally, Compound of Formula I can be prepared at anytemperature in which the starting materials and/or the products arerelatively stable. Typically, the reaction temperature for producingCompounds of Formula I is in the range from about −70° C. to about 130°C. Preferably, the reaction temperature is in the range of from about−70° C. to about 100° C., more preferably from about −30° C. to about70° C., and most preferably from about 0° C. to about 70° C. In oneparticular embodiment of the present invention, the reaction temperatureis at about 40° C. or less, and preferably at about 25° C. or less.

[0117] The reaction time can vary depending on a variety of factorsincluding the reaction temperature, a particular reaction solvent and/orstarting materials used, the amount of each starting material used, andthe concentration of each starting materials. Typically, however, thereaction time is from about 0.5 h to about 48 h, preferably from about0.5 h to about 40 h, and more preferably from about 1 h to about 24 h.

[0118] Because Compounds of Formula I are generally oxygen and/ormoisture sensitive, reactions for producing Compound of Formula I aretypically conducted under an inert atmosphere, preferably a nitrogen,helium or argon atmosphere.

[0119] The present invention also provides a process for preparing anolefin polymer by polymerization of at least one olefin in the presenceof a catalyst component comprising the Compound of Formula I. Thepolymerization can be a homopolymerization or a copolymerization.

[0120] Preference is given to polymerizing an α-olefin, i.e., an olefinof the formula X^(a)X^(b)C═CR^(a)R^(b), where each of X^(a) and X^(b) isindependently hydrogen or a halide, preferably each of X^(a) and X^(b)is independently hydrogen, chloride or fluoride; and each of R^(a) andR^(b) is independently hydrogen, halogen, alkyl, aryl, or cycloalkyl.Exemplary α-olefins include, but not limited to, ethylene, propylene,1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, 1,3-butadiene, 1, 4-hexadiene, acrylates such as methyl acrylate. Otherolefins which can be polymerized using the catalyst component of thepresent invention include non-α-olefins such as cyclic olefinsincluding, but not limited to, cyclopentadiene norbornene,vinylnorbornene, tetracyclododecene, and ethylidenenorbornene.

[0121] The polymerization is preferably carried out at a temperature offrom about −70° C. to about 200° C., particularly preferably from about0 to about 150° C. The polymerization pressure is from about 500 mmHg toabout 50000 mmHg, preferably from about 700 mmHg to about 3500 mmHg. Thepolymerization of an olefin can be carried out continuously orbatchwise, in one or more stages, in solution, in suspension, in the gasphase or in a supercritical medium.

[0122] In a solution polymerization process, suitable solvents includehydrocarbons such as benzene, toluene, hexane, and isooctane.Preferably, the polymerization solvent is toluene or saturatedhydrocarbons. And most preferably, the polymerization solvent isisooctane.

[0123] It is also possible to use mixtures of two or more Compounds ofFormula I. In addition, Compounds of Formula I can also be applied to asolid support. Exemplary solid support materials which are useful in thepresent invention include, but not limited to, activated carbon,alumina, silica, zeolites or polymeric supports described above.Typically, in an olefin polymerization, a Compound of Formula I is usedin a concentration of preferably from about 1 μM to about 1000 μM, morepreferably from about 1 μM to about 100 μM, and most preferably fromabout 5 μM to about 50 μM.

[0124] Prior to addition of the catalyst component, another aluminumalkyl compound, for example, trimethylaluminum, triisobutylaluminum,triethylaluminum, trioctylaluminum, isoprenylaluminum, oralkylaluminoxanes can be added to the reactor to stabilize thepolymerization system (for example, for removing catalyst poisonspresent in the olefin). This is added to the polymerization system in aconcentration of from about 0.01 to about 10 mmol per kg of reactorcontents. For example, triisobutylaluminum or triethylaluminum in aconcentration of from about 0.01 mmol to about 1 mmol per kg of reactorcontents is typically added.

[0125] Compounds of Formula I are also effective co-catalysts for themost of conventional olefin polymerization catalysts. Exemplary olefinpolymerization catalysts, include, but are not limited to,organometallic single site olefin polymerization catalysts, preferablyorganotransition metal single site olefin polymerization catalysts. Asused herein, “organometallic or organotransition metal single siteolefin polymyerization catalysts” refers to a compound comprising ametal or a transition metal, respectively, which is coordinated to atleast one cyclopentadienyl (i.e., Cp) group or its derivative such asmetallocenes. In particular organometallic single site olefinpolymyerization catalysts based on group III, IV, and V metals. Thegroup IV catalysts are typically cationic while the Group IIImetallocene catalysts are typically neutral. Cationic group IV complexesare usually generated by the reaction of neutral group IV complexes withtriaryl carbocation or trialkylammonium salts of weakly coordinatinganions or with large excess of methylaluminoxane (MAO) (e.g., >1000 Alper Zr). Compounds of Formula I are generally soluble in aliphatichydrocarbon solvents and can be used as stoichiometric co-catalysts forgroup IV catalysts, thus eliminating the need for large excess of MAO.The other examples of olefin polymerization catalysts include cationicnickel, palladium and iron complexes comprising diimine and/or phosphineligands. Other useful polymerization catalysts are disclosed in, forexample, U.S. Pat. No. 5, 278, 119, which is incorporated herein byreference in its entirety.

[0126] Additional objects, advantages, and novel features of thisinvention will become apparent to those skilled in the art uponexamination of the following examples thereof, which are not intended tobe limiting.

EXPERIMENTAL

[0127] Experiment 1

[0128] This example illustrates a method for producingAl(CH₃)₂(1-CH₃—CB₁₁F₁₁).

[0129] A mixture of [CPh₃][1-CH₃—CB₁₁F₁₁] (0.300 g, 0.502 mmol) andtoluene (2 ml) was treated with a solution of trimethylaluminum Al(CH₃)₃(0.210 g, 2.92 mmol) in 8 ml of toluene. A mixture was stirred under anitrogen atmosphere for 44 h. During this time a red oil([CPh₃[1-CH₃—CB₁₁F₁₁]) was converted into alight yellow solid. The solidwas then separated by filtration under a nitrogen atmosphere. The solidwas washed 3 times with 1 ml of hexanes and dried under vacuum toprovide 0.184 g (89% yield) of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁).

[0130]¹⁹F NMR (toluene-d₈): δ−252.7; ¹H NMR (toluene-d₈): δ1.47 (3 H),−0.81 (˜6 H);

[0131]¹⁹F NMR (acetonitrile-d₃): δ−251.7 (1 F), −256.2 (5 F), −258.1 (5F);

[0132]¹H NMR (acetonitrile-d₃): δ1.54 (3 H), −0.74, −0.82, and −0.98 (˜6H total);

[0133]¹¹B NMR (acetonitrile-d₃): δ−8.5 (1 B), −16.9 (10 B).

[0134] Experiment 2

[0135] This example illustrates a method for producing a crystallineAl(CH₃)₂(1-CH₃—CB₁₁F₁₁).

[0136] To produce a crystalline Al(CH₃)₂(1-CH₃—CB₁₁F₁₁) compound thereaction described in the Example 1 is performed without stirring. Asolution of trimethylaluminum Al(CH₃)₃ (0.016 g) in 0.5 ml of toluenewas layered over a mixture of [CPh₃][1-CH₃—CB₁₁F₁₁] (0.011 g) and 0.5 mlof toluene. X-ray quality crystals grew on standing at 25° C. for fourdays. The X-ray crystal structure of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁) is shown inFIG. 1.

[0137] Experiment 3

[0138] This example illustrates a method for producingAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁), which is highly soluble in aliphatichydrocarbon solvents (hexanes, methylcyclohexane etc.).

[0139] A suspension of [CPh₃][1-C₁₂H₂₅—CB₁₁F₁₁] (0.030 g, 0.040 mmol) in1 ml of hexanes was treated with a solution of trimethylaluminumAl(CH₃)₃ (0.010 g, 0.139 mmol) in 1 ml of hexanes. The resulting mixturewas stirred for 16 hours and a yellow solution was formed. The yellowsolution was filtered from the traces of a gray solid (˜1-2 mg). Hexanesand an excess of trimethylaluminum were removed under vacuum.Triphenylethane Ph₃CCH₃ was removed from the reaction products bysublimation at 55° C. for 1 h under vacuum (10⁻⁴ torr), leaving ayellow-brown sticky solid (very thick oil). Yield ofAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) was approximately 0.021 g (93%). Thesolubility of Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) in hexanes was at least 0.02 M,and the solubility of Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) in methylcyclohexanewas at least 0.05 M.

[0140]¹⁹F NMR (toluene-d₈): δ−236.9 (1 F), −249.6 (5 F), −250.6 (5 F);

[0141]¹H NMR (toluene-d₈): δ2.43 (2 H), 1.89 (2 H), 1.28 (10 H), 1.16 (6H), 1.05 (2 H), 0.93 (3 H), −0.73 (˜6 H).

[0142]¹⁹F NMR (methylcyclohexane-d₁₄): δ−240.9 (1 F), −246.0 (5 F),−248.3 (5 F);

[0143]¹H NMR (methylcyclohexane-d₁₄): δ2.27 (2 H), 1.78 (2 H), 1.30 (18H), 0.89 (3 H), −0.21 (4 H), −0.42 (2 H).

Experiment 4

[0144] This example illustrates a method for producingAl(C₂H₅)₂(1-CH₃—CB₁₁F₁₁).

[0145] A mixture of (CPh₃][1-CH₃—CB₁₁F₁₁] (7.0 mg) and toluene-d8 (0.4ml) was treated with a solution of triethylaluminum Al(C₂H₅)₃ (10 mg) in0.5 ml of toluene-d₈. During the following 6 days a red oil([CPh₃][1—CH₃-CB₁₁F₁₁]) was disappeared and a clear colorless solutionwas formed. Proton NMR spectrum of the solution indicated thattriphenylmethane CPh₃H and ethane C₂H₄ formed, which is consistent withthe formation of Al(C₂H₅)₂(1-CH₃—CB₁₁F₁₁) (δ¹⁹F −239.8 (1 F), −251.4 (5F) and −251.7 (5 F)) according to the reaction:

[CPh₃][1-CH₃—CB₁₁F₁₁]+Al(C₂H₅)₃→Al(C₂H₅)₂(1-CH₃—CB₁₁F₁₁)+CPh₃H+C₂H₄

[0146] Experiment 5

[0147] This example illustrates a catalytic activity ofAl(CH₃)₂(1-CH₃—CB₁₁F₁₁) for arene-olefin coupling.

[0148] A compound Al(CH₃)₂(1-CH₃—CB₁₁F₁₁) (2 mg) was dissolved in 1 mlof toluene-d₈ and transferred into a sealable NMR tube. The solution wasdegassed under vacuum and treated with 656 torr of ethylene for 14.5hours at 24° C. Proton NMR spectrum of the solution indicated theformation of ethyltoluene. According to the integration of ¹H NMsignals, the molar amount of ethyltoluene produced was approximately 66times larger than the molar amount of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁) present inthe solution. This fact indicated that the formation of ethyltoluene wascatalytic (TON˜66). A GC-MS analysis of the reaction mixture indicatedthe presence of all three positional isomers (i.e., the ortho (47%),meta (35%), and para (18%) isomers) of ethyltoluene C₆D₄(CD₃)(CH₂CH₂D).

[0149] Experiment 6

[0150] This example illustrates a method for producingAl(CH₃)₂((CH₃)₃NB₁₂F₁₁).

[0151] A mixture of [CPh₃][(CH₃)3NB₁₂F₁₁] (29 mg, 45 μmol) andtoluene-d₈ (1.0 ml) was treated with a solution of trimethylaluminumAl(CH₃)₃ (11.0 mg, 150 μmol) in 0.5 ml of toluene-d₈. A mixture wasstirred under a nitrogen atmosphere for 20 h. Proton NMR spectrum of themixture indicated the formation of triphenylethane CPh₃CH₃. A lightyellow solid was then separated from a clear colorless solution byfiltration under a nitrogen atmosphere. The solid was washed 3 timeswith 1 ml of hexanes and dried under vacuum to provide approximately 14mg (68% yield) of Al(CH₃)₂((CH₃)₃NB₁₂F₁₁). The compound was not solublein toluene, but it was completely dissolved in acetonitrile-d₃ withformation of a clear colorless solution.

[0152]¹⁹F NMR (acetonitrile-d₃): δ−259.3 (1 F), −262.9 (10 F);

[0153]¹H NMR (acetonitrile-d₃): δ3.15 (9 H), −0.74, −0.82, and −0.99 (˜6H total).

[0154] Experiment 7

[0155] This example illustrates a catalytic activity ofAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) for polymerization of ethylene.

[0156] A suspension of [CPh₃][1-C₁₂H₂₅—CB₁₁F₁₁] (5.0 mg) in 0.5 ml ofmethylcyclohexane-d₁₄ was treated with 0.5 ml of methylcyclohexane-d₁₄solution of Al(CH₃)₃ (2.2 mg) for 20 h. The solution was filtered fromthe traces of a gray solid. The filtrate was diluted with 7 ml ofhexanes and transferred into a 50 ml Kontes tube. The solution wastreated with 703 torr of ethylene for 18 h at 24° C. and small amount ofwhite solid was formed. The mixture was treated with 3 ml of methanolfor 20 minutes. A solid polyethylene was collected (3 mg) by filtrationand characterized by DSC (T_(m)=126° C.). The activity ofAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) for polymerization of ethylene in hexanessolution at 24° C. was calculated to be approximately 33 g PE/molAl·h·at.

Experiment 8

[0157] This example illustrates that catalytic activity ofAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) for polymerization of ethylene can besignificantly increased by the addition of one equivalent ofbis(cyclopentadienyl)dimethylzirconium Cp₂ZrMe₂.

[0158] A suspension of [CPh₃][1-C₁₂H₂₅—CB₁₁F₁₁] (5.0 mg) in 0.5 ml ofmethylcyclohexane-d₁₄ was treated with 0.5 ml of methylcyclohexane-d₁₄solution of Al(CH₃)₃ (2.2 mg) for 20 h. The solution was filtered fromthe traces of a gray solid. The filtrate was diluted with 7 ml ofhexanes and transferred into a 50 ml Kontes tube. The solution wastreated with 1 ml of hexanes solution of Cp₂ZrMe₂ (1.3 mg). The mixturewas treated with 660 torr of ethylene. The ethylene pressure wasdecreased to 470 torr within 5 minutes due to the formation ofpolyethylene (white solid). More ethylene (812 torr) was added to themixture and the ethylene pressure was decreased to 295 torr within thenext 2 hours. The mixture was quenched with 5 ml of methanol and stirredfor 20 minutes. A solid polyethylene was collected (210 mg) byfiltration and characterized by DSC (T_(m)=129° C.). The catalyticactivity during the first 5 minutes (good agitation) was calculatedbased on the ethylene pressure decrease and was at least 150 kg PE/molZr·h·atm.

[0159] Example 9.

[0160] This example illustrates a catalytic activity ofAl(CH₃)₂(1-CH₃—CB₁₁F₁₁) for the alkylation of benzene with 1-hexene.

[0161] A mixture of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁) (2.5 mg, 4.4 μmol), benzene(0.964 g, 12.4 mmol) and 1-hexene (0.224 g, 2.7 mmol) was stirred for 25hours under a nitrogen atmosphere. A proton NMR spectrum of the reactionmixture indicated that no signals of 1-hexene were present in thereaction mixture after 25 hours. A GC-MS analysis of the reactionmixture indicated the formation of monohexylbenzenes (29%),dihexylbenzenes (20%) and trihexylbenzenes (51%). The relative amountsof 2-phenylhexane and 3-phenylhexane were 70% and 30%, respectively.Total turnovers number of aluminum alkyl catalyst was calculated to beapproximately 606 (24 TON/h).

[0162] It has also been found that Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) is aneffective co-catalyst for the zirconocene catalyzed selectivedimerization of 1-hexene (see Example 10 below). The advantages ofCompounds of Formula I of the present invention toward the conventionalco-catalyst (e.g., MAO) for the similar transformation include theabsence of inductive period, higher total turnovers number of thecatalyst (e.g., 4780 turn over number (TON) compare 500), and higheractivity (315 TONmin⁻¹ compare to 30 TON min⁻¹).

[0163] Example 10.

[0164] This example illustrates that Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) is aneffective co-catalyst for the zirconocene catalyzed selectivedimerization of 1-hexene.

[0165] A solution of Al(CH₃)₂(1-C₂H₂₅—CB₁₁F₁₁) (6.1 mg, 10.8 μmol) in0.28 ml of methylcyclohexane was treated with a solution of Cp₂ZrMe₂(2.3 mg, 9.1 μmol) in 1-hexene (3.654 g). The resulted mixture wasstirred under a nitrogen atmosphere and the samples were taken from thereaction mixture after 5 minutes and 55 minutes. According to ¹H NMRspectra of the reaction mixtures approximately 33% of 1-hexene werereacted within 5 minutes, and approximately 99% of 1-hexene were reactedwithin 55 minutes. The reaction was exothermic as indicated by thesignificant self-heating of the reaction mixture during the reaction.The reaction products were analyzed by ¹H, ¹³C NMR and GC-MS. Accordingto the analysis the reaction mixture contained 83% of 1-hexenedimerization products (more than 95% of 2-butyl-1-octene) and 17% of1-hexene isomerization products (the distribution of hexene isomers wasas follows: E-2 hexene —56%, Z-2 hexene—26%, E-3 hexene—15%, and Z-3hexene—3%). The total turnovers number of the activated zirconocenecatalyst was calculated to be 4780 (87 TONmin⁻¹). The turnovers numberwithin the first five minutes of the reaction was approximately 315TONmin⁻¹

[0166] Example 11

[0167] This example illustrates a method for producing K₂B₁₂F₁₂.

[0168] A 300 mL Monel reactor was charged with K₂B₁₂H₁₂ (0.82. g, 3.73mmol) and hydrogen fluoride was added at −78° C. The reactor was rotatedfor 14 hours at 25° C., warmed up to 70° C. within two hours, and keptat this temperature for 5 hours. The reaction mixture was cooled down to−78° C., degassed and treated with 45 psi of 20% F₂/N₂ mixture. Thereactor was rotated for 6 hours at 25° C. The reaction mixture wascooled down to −78° C., degassed and treated with 45 psi of 20% F₂/N₂mixture. The reactor was rotated for 16 hours at 25° C. and the reactionmixture was treated with 45 psi of 20% F₂/N₂ mixture as described above.The reactor was rotated for 6 hours at 25° C. and the reaction mixturewas treated with 45 psi of 20% F₂/N₂ mixture as described above. Thereactor was rotated for 16 hours at 25° C., cooled down to −78° C. andthe reaction mixture was degassed. Hydrogen fluoride was distilled outunder vacuum and the solid reaction products were dissolved in 50 ml ofwater. The solution was neutralized with a solution of 0.9 g of KOH in10 ml of water. A blue-green precipitate that formed was removed byfiltration and the filtrate (pH˜13-14) was neutralized with H₂SO₄ topH=7. Water was removed from the solution under vacuum and the resultedsolid was treated with 50 ml of acetonitrile. The insoluble material wasremoved by filtration and acetonitrile was removed under vacuum. Theresulted white solid was dried under vacuum at 175° C. for 18 hours toprovide 0.91 g of K₂B₁₂F₁₂ (Yield=56%).

[0169] Example 12

[0170] This example illustrates a method for producing (CPh₃)₂B₁₂F₁₂.

[0171] The compound K₂B₁₂F₁₂ (0.690 g, 1.584 mmol) was dissolved in 15ml of acetonitrile and small amount of white insoluble material wasremoved by filtration. The filtrate was treated with a solution of AgBF₄(0.617 g, 3.167 mmol) in 5 ml of acetonitrile for two hours. A whiteprecipitate that formed was removed by filtration, dried under vacuumand 0.390 g of KBF₄ were collected (98% yield). The filtrate was treatedwith a suspension of CPh₃Cl (0.882 g, 3.167 mmol) in 5 ml ofacetonitrile for 16 hours. A white solid that formed was removed byfiltration, dried under vacuum and 0.385 g of AgCl were collected (85%yield). The filtrate was concentrated down to 10 ml and approximately 40mg of AgCl were collected (9% yield). Acetonitrile was removed from thefiltrate under vacuum. The resulted orange solid was washed with 3×3 mlof dichloromethane, then with 1 ml of hexanes and dried under vacuum toprovide 1.229 g of (CPh₃)₂B₁₂F₁₂ (Yield=92%).

[0172] 1H NNM (acetonitrile-d₃): δ7.72 (6 H), 7.88 (6 H), 8.27 (3 H)

[0173]¹⁹F NMR (acetonitrile-d₃): δ−269.2 (12 F)

[0174] Example 13

[0175] This example illustrates a method for producing((C₁₈H₃₇)Me₂Si)₂B₁₂F₁₂.

[0176] The compound (CPh₃)₂B₁₂F₁₂ (0.067 g, 0.079 mmol) was treated withan excess of (n-C₁₈H₃₇)Me₂SiH (0.8 ml) for one hour at 25° C. and thenfor one hour at 70° C. By that time the orange solid (CPh₃)₂B₁₂F₁₂became a light yellow solid. Hexanes (1 ml) was added to the reactionmixture and the solid was collected by filtration. The solid was washedwith 3×1 ml of hexanes and dried under vacuum to provide 0.070 g ofwhite ((n-C₁₈H₃₇)Me₂Si)₂B₁₂F₁₂ (Yield=90%).

[0177]¹H NMR (benzene-d₆): δ0.17 (6 H), 0.50 (2 H), 0.93 (3 H), 1.04 (2H), 1.16 (2 H), 1.31 and 1.39 (28 H)

[0178]¹⁹F NMR (benzene-d₆): δ−260.1 (12 F)

[0179]¹H NMR (acetonitrile-d₃): δ0.55 (6 H), 0.88 (3 H), 1.00 (2 H),1.27 (32 H)

[0180]¹⁹F NMR (acetonitrile-d₃): δ−269.2 (12 F)

[0181] Example 14

[0182] This example illustrates a method for producing [(n-C₁₂H₂₅)₃NH]₂[B₁₂F₁₂].

[0183] The compound [(n-Bu)₄N]₂[B₁₂F₁₂] (0.150 g, 0.178 mmol) wasdissolved in 50 ml of methanol/acetonitrile 3/1 mixture and elutedthrough a column packed with Amberlist-15 cation exchange resin in itsacidic form. Solvents were removed from elute under vacuum and the oilyresidue was dissolved in 30 ml of water. A viscous liquid (n-C₁₂H₂₅)₃Nwas added to the solution and the mixture was stirred until the viscousliquid disappeared and a white solid was formed (approximately 3 hours).Water was decanted out, the solid was washed with hexanes, collected byfiltration and dried under vacuum at 150° C. for 18 h to provide 0.195 gof [(n-C₁₂H₂₅)₃NH]₂[B₁₂F₁₂] (Yield=78&).

[0184]¹H NMR (toluene-d₈): δ0.97 (9 H), 1.36 (54 H), 1.50 (6 H), 2.82 (6H), 6.02 (1 H)

[0185]¹⁹F NMR (toluene-d₈): δ−266.9 (12 F)

[0186] Example 15

[0187] This example illustrates a method for producing (AlMe₂)₂B₁₂F₁₂.

[0188] The orange microcrystalline compound (CPh₃)₂B₁₂F₁₂ (0.195 g,0.231 mmol) was treated with 2 ml of toluene solution of AlMe₃ (0.161 g,2.240 mmol). Approximately after 5-10 minutes of stirring a red-brownsticky soft solid and a yellow solution were formed. Approximately after5-6 hours of stirring the red-brown sticky solid was disappeared and anamorphous yellow solid was formed. The mixture was stirred foradditional 40 hours. The solid was removed by filtration, washed with 1ml of toluene, then with 3×2 ml of hexanes and dried under nitrogen toprovide 0.106 g of (AlMe₂)₂B₁₂F₁₂ (Yield=97%). The compound was notsoluble in toluene but it was dissolved in acetonitrile-d₃ with theformation of a colorless solution.

[0189]¹ H NMR (acetonitrile-d₃): δ−0.75 and −0.99

[0190]¹⁹F NMR (acetonitrile-d₃): δ−268.7 (12 F)

[0191] Example 16

[0192] This example illustrates a process for synthesizingSi(i-Pr)₃(1-Et—CB₁₁F₁₁).

[0193] A suspension of CPh₃(1-Et—CB₁₁F₁₁) (0.412 g, 0.67 mmol) inpentane (40 ml) was treated with a solution of Si(i-Pr)₃H (0.215 g, 1.36mmol, 2 equiv.) in pentane (10 ml) for 20 hours at room temperature. Themixture was treated with more Si(i-Pr)₃H (0.56 g, 3.54 mmol) for another20 hours. (Note, that a large excess of Si(i-Pr)₃H (˜7 equiv.) requiredfor the reaction to go to completion. A slightly pink pentane solutionwas filtered from a small amount of red-brown oily solid (˜20 mg, whichupon dissolving of in acetonitile was identified as a mixture ofCPh₃(1-Et—CB₁₁F₁₁) and [Si(i-Pr)₃(CD₃CN)][1-Et—CB₁₁F₁₁]. The volume ofthe pentane solution was reduced to ˜5 ml, which caused the formation ofwhite solid. The solid was separated by filtration, washed three timeswith 1 ml of pentane and dried under nitrogen atmosphere inside theglove box. The yield of Si(i-Pr)₃(1-Et—CB₁₁F₁₁) as an off-whitecrystalline solid was 0.198 g (56%). The compound is extremely sensitiveto the traces of water. The color of the solid changed from white toyellow-orange even during storage under nitrogen atmosphere inside theglove box.

[0194] The foregoing discussion of the invention has been presented forpurposes of illustration and description. The foregoing is not intendedto limit the invention to the form or forms disclosed herein. Althoughthe description of the invention has included description of one or moreembodiments and certain variations and modifications, other variationsand modifications are within the scope of the invention, e.g., as may bewithin the skill and knowledge of those in the art, after understandingthe present disclosure. It is intended to obtain rights which includealternative embodiments to the extent permitted, including alternate,interchangeable and/or equivalent structures, functions, ranges or stepsto those claimed, whether or not such alternate, interchangeable and/orequivalent structures, functions, ranges or steps are disclosed herein,and without intending to publicly dedicate any patentable subjectmatter.

References

[0195] 1. Bochmann, M.; Sarsfield, M. J. Organometallics. 1998, 17,5908.

[0196] 2. Aeilts, S. L.; Coles, M. P.; Swenson, D. C.; Jordan, R. F.Organometallics. 1998, 17, 3265.

[0197] 3. Coles, M. P.; Jordan, R. F. J. Am. Chem. Soc. 1997, 119, 8125.

[0198] 4. Ihara, E.; Young, V. G.; Jordan, R. F. J. Am. Chem. Soc. 1998,120, 8277.

[0199] 5. Bruce, M.; Gibson, V. C.; Redshaw, C.; Solan, G. A.; White, A.J. P.; Williams, D. J. Chem. Comm. 1998, 2523.

[0200] 6. Dohmeier, C.; Schnockel, Robl, C, Schneider, Ahlrichs, R.Angew. Chem. Int. Ed. Engl. 1993, 32, 1655.

[0201] 7. Hair, G. S; Cowley, A. H.; Jones, R. A.; McBurnett, B. G.;Voigt, A. J. Am. Chem. Soc. 1999, 121, 4922.

[0202] 8. Jia, C.; Lu, W.; Kitamura, T.; Fujiwara, Y. Organic Letters.1999, 1, 2097.

[0203] 9. Shilov, A. E.; Shul'pin, G. B. Chem. Rev. 1997, 97, 2879.

[0204] 10. Alul, H.; McEwan, G. J. Org. Chem. 1972, 37, 3323.

[0205] 11. Chen, E. Y.; Marks, T. J. Chem. Rev. 2000, 100, 1391.

What is claimed is:
 1. A compound of the formula: M_(x)Q_(y), whereineach M is independently a cation, provided at least one M is a reactivecation selected from the group consisting of silver cation, aluminumcation, silylium cation, ammonium cation, protonated arene, and triarylcarbocation; Q is a polyhalogenated polyhedral borate of the formula(B₁₂X₁₂)⁻² or a fluorinated polyhedral borate moiety selected from thegroup consisting of monoheteroborate and aminoborate, provided when Q isa monoheteroborate then M is an aluminum cation; each X is independentlyhalide; x is an absolute value of the oxidation state of Q; and y is anabsolute value of the oxidation state of M.
 2. The compound of claim 1,wherein said aluminum cation is a moiety of the formula (R¹R²Al)⁺¹,wherein each of R¹ and R² is independently selected from the groupconsisting of alkyl, cycloalkyl, aryl, aralkyl, cycloalkalkyl, alkenyl,and halide.
 3. The compound of claim 1, wherein said silylium cation isa moiety of the formula (R³R⁴R⁵Si)⁺¹, wherein each of R³, R⁴, and R⁵ isindependently selected from the group consisting of hydrogen, alkyl,aryl, aralkyl, cycloalkyl, and-halide.
 4. The compound of claim 1,wherein said ammonium cation is a moiety of the formula (R¹⁶R¹⁷R¹⁸NH)⁺¹,wherein each of R¹⁶, R¹⁷, and R¹⁸ is independently selected from thegroup consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl, andsilyl.
 5. The compound of claim 4, wherein each of R¹⁶, R¹⁷, and R¹⁸ isindependently selected from the group consisting of alkyl, aryl,aralkyl, and cycloalkyl.
 6. The compound of claim 1, wherein saidmonoheteroborate is of the formula((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f))⁻¹, wherein R⁶ is bonded to Z, Zis bonded to B, and each of H, F, X, and OR⁷ is bonded to a differentboron atom, and wherein R⁶ is selected from the group consisting ofpolymer, hydrogen, halide, alkyl, cycloalkyl, alkenyl, alkynyl, andaryl; Z is selected from the group consisting of C, Si, Ge, Sn, Pb, N,P, As, Sb, and Bi; each X is independently halide; R⁷ is selected fromthe group consisting of polymer, hydrogen, alkyl, cycloalkyl, alkenyl,alkynyl, and aryl; a is 0 or 1; b is an integer from 5 to 13; c is aninteger from 0 to 12; d is an integer from 2 to 13; e is an integer from0 to 11; f is an integer from 0 to 5; and the sum of c+d+e+f is b. 7.The compound of claim 1, wherein said aminoborate is a moiety of theformula (R⁸R⁹R¹⁰NB_(g)H_(h)F_(i))⁻¹, wherein R⁸, R⁹, and R¹⁰ are bondedto N, and N is bonded to boron, and each of H and F is bonded to adifferent boron atom, and wherein each of R⁸, R⁹, and R¹⁰ isindependently selected from the group consisting of hydrogen, alkyl,cycloalkyl, aryl, aralkyl, and a polymer; g is an integer from 6 to 14;h is an integer from 0 to 13; i is an integer from 1 to 14; and the sumof 1+h+i is g.
 8. The compound of claim 1, wherein Q is saidpolyhalogenated borate of the formula (B₁₂X₁₂)⁻², wherein X that definedin claim
 1. 9. The compound of claim 8, wherein said halide is selectedfrom the group consisting of Cl and F.
 10. The compound of claim 8,wherein said polyhalogenated borate comprises at least three fluorides.11. The compound according to claim 1 of the formula(R¹R²Al)[(R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)].
 12. The compoundaccording to claim 11, wherein Z is C and a is
 1. 13. The compoundaccording to claim 12, wherein R⁶ is selected from the group consistingof alkyl, aryl, and silyl.
 14. The compound according to claim 13,wherein c, e, and f are
 0. 15. The compound according to claim 14,wherein b and d are
 11. 16. The compound according to claim 15, whereinR⁶ is selected from the group consisting of methyl, ethyl, dodecyl,butyl, iso-butyl, t-butyl, silyl, propyl, iso-propyl, pentyl, hexyl, anda polymer.
 17. The compound according to claim 11, wherein each of R¹and R² is independently selected from the group consisting of alkyl,aryl, and halide.
 18. The compound according to claim 17, wherein R¹ andR² are methyl, ethyl, iso-propyl, propyl, butyl, iso-butyl, t-butyl,pentyl, hexyl, and halide.
 19. The compound according to claim 1 of theformula (R¹R²Al)[R⁸R⁹R¹⁰N—B_(g)H_(h)F_(i)].
 20. The compound accordingto claim 19, wherein g is 12, i is 11 and h is
 0. 21. The compoundaccording to claim 20, wherein R⁸, R⁹, and R¹⁰ are alkyl.
 22. Thecompound according to claim 21, wherein each of R⁸, R⁹, and R¹⁰ isindependently selected from the group consisting of methyl, ethyl,hexyl, octyl, and dodecyl.
 23. The compound according to claim 22,wherein each of R¹ and R² is independently selected from the groupconsisting of alkyl, aryl, and halide.
 24. The compound according toclaim 23, wherein each of R¹ and R² is independently selected from thegroup consisting of methyl, ethyl, iso-propyl, propyl, butyl, iso-butyl,t-butyl, pentyl, hexyl, and halide.
 25. A catalyst component comprisinga compound of the formula: M_(x)Q_(y), wherein each M is independently acation, provided at least one M is a reactive cation selected from thegroup consisting of silver cation, aluminum cation, silylium cation,ammonium cation, protonated arene, and triaryl carbocation; Q is apolyhalogenated polyhedral borate or a fluorinated polyhedral boratemoiety selected from the group consisting of monoheteroborate andaminoborate; x is an absolute value of the oxidation state of Q; and yis an absolute value of the oxidation state of M.
 26. The catalystcomponent according to claim 25, wherein said compound is selected fromcompounds of the formula: (i)(R¹R²Al)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)); (ii)(R³R⁴R⁵Si)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)); (iii)(R¹⁶R¹⁷R¹⁸NH)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)) (iv)(Ar¹H)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)); (v)(Ar²Ar³Ar⁴C)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)); and (vi)Ag((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)), wherein R⁶ is bonded to Z, Zis bonded to B, and each of H, F, X, and OR⁷ is bonded to a differentboron atom, and wherein each of Ar¹, Ar², Ar³, and Ar⁴ is independentlyan optionally substituted aryl; each of R¹ and R² is independentlyselected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl,cycloalkalkyl, alkenyl, and halide; each of R³, R⁴, and R⁵ isindependently selected from the group consisting of hydrogen, alkyl,aryl, aralkyl, cycloalkyl, and halide; R⁶ is selected from the groupconsisting of polymer, hydrogen, halide, alkyl, cycloalkyl, alkenyl,alkynyl, and aryl; each of R¹⁶, R¹⁷, and R¹⁸ is independently selectedfrom the group consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl,and silyl; Z is selected from the group consisting of C, Si, Ge, Sn, Pb,N, P, As, Sb, and Bi; each X is independently halide; R⁷ is selectedfrom the group consisting of polymer, hydrogen, alkyl, cycloalkyl,alkenyl, alkynyl, and aryl; a is 0 or1; b is an integer from 5 to 13; cis an integer from 0 to 12; d is an integer from 2 to 13; e is aninteger from 0 to 11; f is an integer from 0 to 5; and the sum ofc+d+e+f is b.
 27. The catalyst component according to claim 26, whereinZ is C and a is
 1. 28. The catalyst component according to claim 27,wherein c, e, and f are
 0. 29. The catalyst component according to claim28, wherein b and d are
 11. 30. The catalyst component according toclaim 25, wherein said compound is selected from compounds of theformula: (i) (R¹R²Al)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)); (ii)(R³R⁴R⁵Si)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)); (iii)(R¹⁶R¹⁷R¹⁸NH)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)) (iv)(Ar¹H)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)); (v)(Ar²Ar³Ar⁴C)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)); and (vi)Ag(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)), wherein R⁸, R⁹, and R¹⁰ are bonded to N,and N is bonded to boron, and each of H and F is bonded to a differentboron atom; and wherein each of Ar¹, Ar², Ar³, and Ar⁴ is independentlyan optionally substituted aryl; each of R¹ and R² is independentlyselected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl,cycloalkalkyl, alkenyl, and halide; each of R³, R⁴, and R⁵ isindependently selected from the group consisting of hydrogen, alkyl,aryl, aralkyl, cycloalkyl, and halide; each of R⁸, R⁹, and R¹⁰ isindependently selected from the group consisting of hydrogen, alkyl,cycloalkyl, aryl, aralkyl, and a polymer; each of R¹⁶, R¹⁷, and R¹⁸ isindependently selected from the group consisting of hydrogen, alkyl,aryl, aralkyl, cycloalkyl, and silyl; g is an integer from 6 to 14; h isan integer from 0 to 13; i is an integer from 1 to 14; and the sum of1+h+i is g.
 31. The catalyst component according to claim 30, wherein gis 12, i is 11 and h is
 0. 32. The catalyst component according to claim25, wherein said compound is selected from compounds of the formula: (i)(M¹)_(m)(R¹R²Al)_(n)(B₁₂X₁₂); (ii) (M¹)_(m)(R³R⁴R⁵Si)_(n)(B₁₂X₁₂); (iii)(M¹)_(m)(R¹⁶R¹⁷R¹⁸N)_(n)(B₁₂X₁₂) (iv) (M¹)_(m)(Ar¹H)_(n)(B₁₂X₁₂); (v)(M¹)_(m)(Ar²Ar³Ar⁴C)_(n)(B₁₂X₁₂); and (vi) (M¹)_(m)Ag_(n)(B₁₂X₁₂),wherein M¹ is a non-reactive cation; each of Ar¹, Ar², Ar¹, and Ar⁴ isindependently an optionally substituted aryl; each of R¹ and R² isindependently selected from the group consisting of alkyl, cycloalkyl,aryl, aralkyl, cycloalkalkyl, alkenyl, and halide; each of R³, R⁴, andR⁵ is independently selected from the group consisting of hydrogen,alkyl, aryl, aralkyl, cycloalkyl, and halide; each of R¹⁶, R¹⁷, and R¹⁸is independently selected from the group consisting of hydrogen, alkyl,aryl, aralkyl, cycloalkyl, and silyl; each X is independently a halide;m is 0 or1; n is 1 or 2, provided the sum of m and n is
 2. 33. Thecatalyst component according to claim 32, wherein each X isindependently selected from the group consisting of Cl and F.
 34. Thecatalyst component according to claim 33, wherein at least three of saidhalide is fluoride.
 35. The catalyst component according to claim 34,wherein X is fluoride.
 36. A process for preparing an olefin polymer bypolymerization of at least one olefin in the presence of a catalystcomponent, wherein said catalyst component comprises a compound of theformula: M_(x)Q_(y), wherein each M is independently a cation, providedat least one M is a reactive cation selected from the group consistingof silver cation, aluminum cation, silylium cation, ammonium cation,protonated arene, and triaryl carbocation; Q is a polyhalogenatedpolyhedral borate of the formula (B₁₂X₁₂)⁻² or a fluorinated polyhedralborate moiety selected from the group consisting of monoheteroborate andaminoborate; X is a halide; x is an absolute value of the oxidationstate of Q; and y is an absolute value of the oxidation state of M. 37.The process of claim 36, wherein said olefin is an α-olefin.
 38. Aprocess for coupling an olefin to an aryl compound comprising: (a)contacting an aryl compound of the formula: R¹¹H with a metal complex ofthe formula: M¹ _(m)(R¹R²Al)_(n)Q_(q) to form a hydrocarbylaluminumcomplex selected from the group consisting of a compound of the formula:M¹ _(m)(R¹R¹¹Al)_(n)Q_(q), M¹ _(m)(R²R¹¹Al)_(n)Q_(q), M¹_(m)[(R¹¹)₂Al]_(n)Q_(q), and mixtures thereof, and (b) contacting saidhydrocarbylaluminum complex with an olefin of the formula:R¹²R¹³C═CR¹⁴R¹⁵ to form an alkyl substituted aryl compound of theformula: R¹¹R¹²R¹³C—CHR¹⁴R¹⁵ wherein each of R¹ and R² is independentlyselected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl,alkenyl, and halide; and Q is a polyhalogenated polyhedral borate of theformula (B₁₂X₁₂)⁻² or a fluorinated polyhedral borate moiety selectedfrom the group consisting of: (i) monoheteroborate of the formula(R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f), wherein R⁶ is bonded to Z, Z isbonded to B, and each of H, F, X, and OR⁷ is bonded to a different boronatom; and (ii) aminoborate of the formula R⁸R⁹R¹⁰NB_(g)H_(h)F_(i),wherein R⁸, R⁹, and R¹⁰ are bonded to N, and N is bonded to boron, andeach of H and F is bonded to a different boron atom; wherein R⁶ isselected from the group consisting of polymer, hydrogen, halide, alkyl,cycloalkyl, alkenyl, alkynyl, and aryl; Z is selected from the groupconsisting of C, Si, Ge, Sn, Pb, N, P, As, Sb, and Bi; each X isindependently halide; R⁷ is selected from the group consisting ofpolymer, hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; eachof R⁸, R⁹, and R¹⁰ is independently selected from the group consistingof hydrogen, alkyl, cycloalkyl, aryl, aralkyl, and a polymer; R¹¹ isaryl; each of R¹², R¹³, R¹⁴ and R¹⁵ is independently selected from thegroup consisting of hydrogen, alkyl, aryl, cycloalkyl, aralkyl,cycloalkakyl, halide, and a polymer; M¹ is a non-reactive cation; m is 0or 1; n is 1 or 2, provided the sum of m+n is an absolute value of theoxidation sate of Q; q is an absolute value of the total oxidation stateof M¹ and (R¹R²Al)⁺¹; a is 0 or 1; b is an integer from 5 to 13; c is aninteger from 0 to 12; d is an integer from 2 to 13; e is an integer from0 to 11; f is an integer from 0 to 5; g is an integer from 6 to 14; h isan integer from 0 to 13; i is an integer from 1 to 14; the sum ofc+d+e+f is b; and the sum of 1+h+i is g.
 39. A process for producing afluoroborate salt comprising a reactive cation, said process comprisingthe steps of: (i) fluorinating a non-fluorinated compound of the formulaM¹ _(p)Q_(q) ¹ by contacting said non-fluorinated compound with HF, F₂or mixtures thereof under conditions sufficient to produce a fluorinatedsalt of the formula M¹ _(p)Q_(q), wherein each M¹ is a non-reactivecation; Q¹ is a nonfluorinated polyhedral borate moiety selected fromthe group consisting of monoheteroborate, aminoborate, andpolyhalogenated borate; Q is a fluorinated Q¹; and p is an absolutevalue of the oxidation state of Q¹; q is an absolute value of theoxidation state of M¹, and (ii) exchanging said non-reactive cation witha reactive cation to produce a fluorinated salt of the formulaM_(p)Q_(q), wherein each M is independently a cation, provided at leastone M is a reactive cation selected from the group consisting of silvercation, aluminum cation, silylium cation, ammonium cation, protonatedarene, and triaryl carbocation, provided when Q¹ is a monoheteroboratethen at least one of the M is an aluminum cation.
 40. The process ofclaim 39, wherein said reactive cation is a triaryl carbocation.
 41. Theprocess of claim 40, wherein said cation exchange step comprisescontacting said fluorinated salt of the formula M¹ _(p)Q_(q) with atriaryl carbocation boron tetrafluoride under conditions sufficient toexchange said non-reactive cation with said triaryl carbocation, whereinM¹, Q, p, and q are those defined in claim
 39. 42. The process of claim40, wherein said cation exchange step comprises the steps of: (a)contacting said fluorinated salt of the formula M¹ _(p)Q_(q) with silverboron tetrafluoride to produce a silver salt of the formula(M¹)_(m)Ag_(n)Q_(q), wherein M¹, Q, p, and q are those defined in claim39; m is 0or 1; n is 1 or 2, provided the sum of m+n is an absolutevalue of the oxidation state of Q; and (b) contacting said silver saltwith a triaryl halide under conditions sufficient to exchange saidsilver cation with said triaryl carbocation.
 43. The process of claim39, wherein said reactive cation is silver cation.
 44. The process ofclaim 43, wherein said cation exchange step comprises the steps ofcontacting said fluorinated salt of the formula M¹ _(p)Q_(q) with silverboron tetrafluoride under conditions sufficient to exchange saidnon-reactive cation with said silver cation, wherein M¹, Q, p, and q arethose defined in claim
 39. 45. The process of claim 39, wherein saidreactive cation is selected from the group consisting of (a) silyliumcation of the formula (R³R⁴R⁵Si)⁺¹, wherein each of R³, R⁴, and R⁵ isindependently selected from the group consisting of hydrogen, alkyl,aryl, aralkyl, cycloalkyl, and halide; and (b) aluminum cation of theformula (R¹R²Al)⁺¹, wherein each of R¹ and R² is independently selectedfrom the group consisting of alkyl, cycloalkyl, aryl, aralkyl,cycloalkalkyl, alkenyl, and halide.
 46. The process of claim 45, whereinsaid cation exchange step further comprises the steps of: (a) convertingsaid fluorinated salt of the formula M¹ _(p)Q_(q) to a fluorinated saltcomprising a triaryl carbocation, wherein M1, Q, p and q are thosedefined in claim 39; and (b) contacting said triaryl carbocationcomprising fluorinated salt with a compound of the formula R³R⁴R⁵SiH orR¹R²AlR¹⁹ under conditions sufficient to produce a fluorinated compoundof the formula (M¹)_(m)(r³R⁴R⁵Si)_(n)Q_(q) or (M¹)_(m)(R¹R²Al)_(n)Q_(q),respectively, wherein R¹⁹ is selected from the group consisting ofhydrogen and alkyl; m is 0 or 1; n is 1 or 2, provided the sum of m+n isan absolute value of the oxidation state of Q; M¹, Q, p and q are thosedefined in claim 39; and R¹, R², R³, R⁴, and R⁵ are those defined inclaim
 45. 47. The process of claim 39, wherein said reactive cation isan ammonium cation of the formula (R¹⁶R¹⁷R¹⁸NH)⁺¹, wherein each of R¹⁶,R¹⁷, and R¹⁸ is independently selected from the group consisting ofhydrogen, alkyl, aryl, aralkyl, cycloalkyl, and silyl.
 48. The processof claim 47, wherein said cation exchange step further comprises thesteps: (a) acidifying said fluorinated salt of the formula M¹ _(p)Q_(q)under conditions sufficient to produce acidic fluorinate salt of theformula (M¹)_(m)H_(n)Q_(q); and (b) contacting said acidic fluorinatedsalt with an amine of the formula R¹⁶R¹⁷R¹⁸N to produce an ammoniumfluorinated borate salt of the formula (M¹)_(m)(R¹⁶R¹⁷R¹⁸NH)_(n)Q,wherein R¹⁶, R¹⁷, and R¹⁸ are those defined in claim 47, m is 0 or 1; nis 1 or 2, provided the sum of m+n is an absolute value of the oxidationstate of Q; and M¹, Q, p and q are those defined in claim
 39. 49. Theprocess of claim 39, wherein said reactive cation is a protonated areneof the formula (Ar¹H)⁺¹, wherein Ar¹ is an optionally substituted aryl.